Epoxy resin mixtures containing heterocyclic systems

ABSTRACT

EPOXIDE RESIN MIXTURES, WHICH AT ROOM TEMPERATURE ARE STABLE TO STORAGE AND DO NOT CRYSTALLISE, OF (A) DIGLYCIDYL ETHERS OF BINUCLEAR 5-MEMBERED OR 6-MEMBERED, UNSUBSTITUTED OR SUBSTITUTED, OXYALKYLATED N-HETEROCYCLID COMPOUNDS WHICH CONTAINS TWO NH GROUPS IN THE MOLECULE FOR EXAMPLE 1,6 - BIS(1&#39;&#39; - GLYCIDYLOXETHYL-5&#39;&#39;,5&#39;&#39;-DIMETHYLHYDANTOINYL)-HEXANE, AND (B) POLYGLYCIDYL COMPOUNDS OF THE N-HETEROCYCLIC SERIES WHICH CONTAIN AT LEAST ONE HETEROCYCLIC RING, WHICH POSSESSES THE -NH-CO- GROUPING AT LEAST ONCE, WITH AT LEAST TWO GLYCIDYL GROUPS OR BMETHYLGLYCIDYL GROUPS IN THE POLYGLYCIDYL COMPOUNDS BEING LINKED DIRECTLY TO ENDOCYCLIC NITROGEN ATOMS (FOR EXAMPLE 1,3-DIGLYCIDYL-5,5-DIMETHYLHYDANTOIN).

United States Patent "i 3,133,282

Patented May 15,, 1973 wherein R, R", R", and R" each represents amember EPOXY RESIN $73 351?? 8 CONTAINING selected from the groupconsisting of alkyl with 1 to 5 HET C C SYSTEMS carbon atoms, alkenylw1th 1 to 5 carbon atoms, cyclohexyl, cyclohexenyl, phenyl andsubstituted phenyl, or

Juergen Habermeler, Allschwll, Hans Batzer, Arleshelm, 5 when theradical Z1 or Z2 represents the formula and Daniel Porret, Binningen,Switzerland, assignors to Ciba-Geigy AG., Basel, Switzerland No Drawing.Filed Mar. 24, 1971, Ser. No. 127,766 Claims priority, applicationSwitzerland, Apr. 1, 1970, C

4,792/70 Int. Cl. C08g 45/06 10 US. Cl. 260-830 TW 5 Claims R and R"together can also form a member selected from the group consisting ofdivalent tetramethylene and ABSTRACT OF THE DISCLOSURE pentanethyleneradical, A represents a divalent aliphatic,

Epoxide rain mixtures, which at room temperature are cycloaliphatic oraraliphatic radical, and in particular stable to storage and do notcrystallise, of (a) diglycidyl preferably represents an al-kyleneradical, or an alkylene ethers of binuclear S-membered or 6-membered,unsubradical interrupted by oxygen atoms, X X Y and Y stituted orsubstituted, oxyalkylated N-heterocyclic comeach denote a hydrogen atomor a methyl group, and m pounds which contain two NH groups in themolecule and n each represent an integer having a value of 0 to 30,

for example 1, 6 bis(1' glycidyloxyethyl-S',5-dimethylpreferably of 0 to4, with the sum of m and it having to hydantoinyl)-hexane, and (b)polyglycidyl compounds of be at least 1.

the N-heterocyclic series which contain at least one heter- Thecompounds of the Formula I are manufactured by ocyclic ring, whichpossesses the NH-CO-- grouping reacting compounds of the general formulamethylglycidyl groups in the polyglycidyl compounds ing as in theFormula I, in one stage or several stages, being linked directly toendocyclic nitrogen atoms (for with an epihalogenohydrinor'fl-methylepihalogenohydrin, example1,3-diglycidyl-5,5-dimethylhydantoin). such as, for example,epichlorohydrin, B-methylepichlorohydrin or epibromohydrin, in a mannerwhich is in itself I known.

BACKGROUND OF THE INVENTION The compounds of the Formula I can be curedwith The subject of Swiss Pat. No. 510,689 are new di- 40 the customarycuring agents for polyepoxide compounds glycidyl compounds of thegeneral formula: to give moulded materials.

ll l Cr-(f-Cfiz- O(lJH-OH2) fiC-N\ A N-\ (CHz-(|3HO GHi i'1 -CH7 X1 Y1:71 Zr /C=O O=C Z7 Y2 X2 wherein Z and Z independently of one anothereach DETAILED DESCRIPTION denote a nitrogen-free divalent radical whichis required I l 1 f to complete a S-membered or 6-membered,unsubstituted It has now been found that P ded g l' s or substitutedheterocyclic ring having the formulae tlcularly advantage pr P are 0tamed. 1f I tures of epoxide compounds of the Formula I, 1n whrch 6 theglycidyl groups are bonded to the N-heterocyclic rings 0:0; 0 I [B H viaa mobile chain, and polyglycidyl compounds of the I N-heterocyclicseries, which contain at least one hetero- /o cyclic ring, whichpossesses the -N--C- and I R! grouping at least once, with at least twoglycidyl groups or B-methylglycrdyl groups in the poly-glycldylcompounds being directly linked to endocyclic nitrogen atoms, that is tosay with the glycidyl groups being directly bonded to the rigidN-heterocyclic ring, are cured with a curing agent for epoxide resins,especially with a polycarboxylic acid anhydride.

The mixtures of the abovementioned epoxide compounds are preferablyliquids and are hence easily processable. If polyglycidyl compounds ofthe N-heterocyclic series which crystallise easily are used, they can beprevented from crystallising out of the mixture by adding a littledicarboxylic acid anhydride which effects a partial pre-addition of theglycidyl compounds. It is, however, also possible to use solventscontaining epoxide groups, such as N-glycidyloxazolidin-2-ones, toprevent the crystallisation of the N-glycidyl compounds from themixtures mentioned. The mixtures thus manufactured are liquid epoxideresins which are stable to storage and do not crystallise. It is on theother hand, however, also possible to mix the appropriate abovementionedepoxide resins only directly before adding the curing agent.

The subject of the present invention are therefore curable mixtureswhich are suitable for the manufacture of shaped articles, includingsheet-like structures, characterised in that they contain (a) diglycidylethers of the general formula wherein Z and Z independently of oneanother each denote a nitrogen-free divalent radical which is requiredto complete a 5-membered or 6-membered, unsubstituted or substitutedheterocyclic ring having the formula wherein R, R, R' and R" eachrepresents a member selected from the group consisting of alkyl with 1to 5 carbon atoms, alkenyl with 1 to 5 carbon atoms, cyclohexyl,cyclohexenyl, phenyl and substituted phenyl, or when the radical Z or Zrepresents the formula R and R" together can also form a member selectelfrom the group consisting of divalent tetramethylene and pentaethyleneradical. A represents a divalent aliphatic, cycloaliphatic oraraliphatic radical, and in particular preferably represents an alkyleneradical, or an alkylene radical interrupted by oxygen atoms, X X Y and Yeach denote a hydrogen atom or a methyl group, and m and I: eachrepresent an integer having a value of 0 to 30, preferably of 0 to 4,with the sum of m and 11 having to be at least 1, (b) polyglycidylcompounds of the N-heterocyclic series which contain at least 1heterocyclic ring which possesses the grouping at least one, with atleast two glycidyl groups or SI-methacid anhydride, and also,optionally, a curing catalyst.

4 Polyglycidyl compounds of the N-heterocyclic series (b) areconveniently obtainable according to known methods, by reaction ofepichlorohydrin or B-methylepichlorohydrin with heterocyclic ureaderivatives, such as, especially, cyanuric acid, ethyleneurea,hydantoin, substituted hydantoins, bis(hydantoin) compounds, uracil,

substituted uracils, dihydrouracils, or bis(dihydrouracil) compounds, inthe presence of suitable catalysts, for example tertiary amines.

Compounds which may be mentioned are the triglycidylisocyanurate of theformula N,N-diglycidyl-parabanic acid; N,N'-diglycidyl compounds of theformula HzC\CHCHaN N-CHzCH--CH2 o HzC-(CHz)n 0 (III) wherein n=1 or 2,that is to say N,N'-diglycidylpropyleneurea and above allN,N-diglycidylethyleneurea (=1, 3-diglycidylimidazoline-2);N,N'-diglycidy1 compounds of the formula wherein R and R each denote ahydrogen atom or a lower alkyl radical with 1 to 4 carbon atoms, orwherein R and R together form a tetramethylene or pentamethyleneradical; representatives of this class of compound are, for example:

1,3-diglycidylhydantoin, 1,3-diglycidyl-5-methyl-hydantoin,1,3-diglycidyl-S-n-propyl-hydantoin,1,3-diglycidyl-5-methyl-S-ethyI-hydanto-in,1,3-diglycidyl-1,3-diaza-spiro (4.5) -decane-3,4-dione, 1,3-diglycidyl-1 ,3-diazaspiro (4.4 -nonane-2,4-dione and especiallyl,3-diglycidyl-5,S-dimethyl-hydantoin as well as1,3-diglycidyl-S-isopropoyl-hydantoin.

wherein R R R and R each denote a hydrogen atom or a lower alkyl radicalwith 1 to 4 carbon atoms, or wherein R and R and/or R and R togetherform a tetramethylene or pentamethylene radical; representatives of thisclass of compound are, for example, bis-(3-glycidyl 5,5dimethyl-hydantoinyl)-1)-methane, bis-(3- 5glycidyl-S-methyl-S-ethyl-hydantoinyl-1) methane andbis-(3-glycidyl-S-propyl-hydrantoinyl-1)-methane.

wherein R R R and R independently of one another each denote a hydrogenatom or a lower alkyl radical with 1 t 4 carbon atoms; representativesof this class of compound are, for example,3,3'-diglycidy1-1,1'-methylone-bis(5,6-dihydrouracil),3,3-diglycidyl-1,1'-methylene- O R3 0 bis(6-methyl-5,G-dihydro-uracil)and 3,3'-diglycidyl-1,1'-

C NR-N C methylene-bis-(5,5-dimethyl-5,6-dihydrouracil). The mixingratios of the two abovementioned epoxide ll components (a) and (b)depend on the particular end 0 P 10 use. For many cases, mixtures of 1mol of the epoxide wherein R is an aliphatic, cycloaliphatic oraraliphatic compound d 1 l of h id compound (b) radical and 1 2 3 and 4Bach denote a hydrogen prove the most suitable, since the shapedarticles obatom or a lower alkyl radical with 1 to 4 carbon atoms, mi dtherefrom b curing couple gQod e h ni l or wherein 1 and 2 and/01 3 and4 together form strengths with a certain flexibility, whilst retaininggood a tetramethylene or pentamethylene radical; representah resistance,tives of this Class Of compound for p However, optimum properties canalso be achieved bis(1 glycidyl s,5 dimethy1hydam0iny1 3) methane withother m xing ratios, depending on the nature of the 1,2-bis(1'-glycidyl-5 ',5-dimethylhydantoinyl-3 ethane, comblned reslnsl4 bi (1gly idy1 5 5 di thylhyd t i y1 3 )b t a, The mixtures of theabovementioned epoxrde com- 1,6-bis(1'-glycidyl-5',5'-dimethylhydantoinyl-3')hexane, P0111148 and (b) are preferably curedwith polycarl,l2 bis(1' g1ycidy1 5I5/ dimethy1hydant0iny1 3I) boxyhcacld anhyclndes. However, curing with polyammes dodecane and is alsopossible. B,l3, biS(1 g1ycidy1 5',5' dimethy1hydantoiny1 3' )diethYL Thecurable epoxide resin m xtures can furthermore be ethen mixed, in anystage before curing, with customary modi- N,N, diglycidyl compounds ofthe formula fiers, such as extenders, fillers and reinforcing agents,mg- 0 ments, dyestuffs, organic solvents, plasticisers, fiow controlagents, agents for conferring thixotropy flameproofing O substances ormould release agents. gl The curable epoxide resin mixtures according tothe invention are above all employed in the fields of surface R5-protection, the electrical industry, laminating processes and thebuilding industry. (VII) hln the egrample which followls, unlessotherwise stated, t e parts enote parts by weig t and percentages denoteofby to 4 carbon atoms: representatives of this class of comto parts ywelg Us as of the mllhhtre to the gram' pound are, for example,1,3-diglycidyl-uracil, 1,3-digly- E l cidyl-6-methyl-uracil, and1,3-diglycidyl-S-methyl-uracil.

N,N' dig1ycidy1 compounds f the f l 60 parts of1,6-b1s-(l-glyc1dyloxyethyl-5',5'-d1methyl- O 40 hydanto1nyl-3')-hexane(epoxide content 3.71 equivalents/kg.) are mixed with 27.2 parts of1,3-diglycidyl- 0 5,5-dimethylhydantoin (epoxide content 8.0equivalents/ gfi kg.). A homogeneous melt is obtained by Warming to 70RP 0:0 C., and is vigorously stirred at this temperature for some timefurther. After cooling, a clear, pale yellow, non- 3 crystallising resinis obtained.

(V111) 62.0 parts of hexahydrophthalic anhydride and 0.2 g. wherein Rand R denote identical or dilferent alkyl of benzyldliriethylamme added.thereto after radicals, preferably methyl groups and R3 and R4 thoroughmix ng the whole is poured mt casting moulds dependently of one anothereach denote a hydrogen atom lgade 9 E g g g to 9 cungg takes or an alkylradical (R is preferably an alkyl radical with p 10 (LUIS t C at nsubse' 1 to 4 carbon atoms and R is preferably hydrogen). quen th ye cRepresentatives of this class of compound are, for exf a mgs avmg e 0Owing properties are 0 ample,1,3-diglycidyl-5,5-dimethyl-5,6-dihydro-uracil and1,3-diglycidyl-d,5-dimethyl-6-isopropyl-5,6-dihydro-uracil. TensileStrength (VSM 77 0 2 708 y y compounds of the formula Elongation atbreak (VSM 77,101 percent 2 0 o Flexural strength (VSM 77,103) kp./mm.13.6 l 0 Deflection (VSM 77,103) mm 8.8 Flexural impact strength (VSMOH2CHCH2-N N-- z-N N z0 77,105 k 2 0.13

0: H --R5 R7-CH =0 C We claim:

| 1. A composition of matter which comprises (a) di- 0 R8 glycidylethers of the general formula 0 0 II Ofir COHz OCHCI-Iz N/ \IIIAIII/N-(CHzFHO) CH2-(l3 CHa I Ci 31H )m Z1 Z2 3 Ya 1; X2

and

/ RIIII wherein R, R, R' and R"" each represents a member selected fromthe group consisting of alkyl with 1 to 5 carbon atoms, alkenyl with 1to 5 carbon atoms, cyclohexyl, cyclohexenyl, phenyl and substitutedphenyl, or when the radical Z or Z represents the formula R' and R"together can also form a member selected from the group consisting ofdivalent tetramethylene and pentanethylene radical, and m and 11 eachrepresent an integer having a value of 0 to 4, with the sum of m and 11having to be at least 1, (b) polyglycidyl compounds of theN-heterocyclic series which contain at least 1 heterocyclic ring whichpossesses the grouping N C l H at least one, with at least two glycidylgroups or B-methyL glycidyl groups in the polyglycidyl compounds beingdirectly linked to endocyclic nitrogen atoms, and (c) a curing agent forepoxide resins, especially a polycarboxylic acid anhydride, and also,optionally, a curing catalyst.

2. A composition as claimed in claim 1, which contains 1,6 bis(l'-glycidyloxyethyl-5',5-dimethyl-hydantoinyl-3'-hexane as the epoxide(a).

3. A composition as claimed in claim 1, which contains1,3-diglycidyl-5,5-dimethylhydantoin as the epoxide (b).

4. A composition as claimed in claim 1, which contains a polycarboxylicacid anhydride as the curing agent (c).

5. A composition as claimed in claim 4, which contains hexahydrophthalicanhydride as the polycarboxylic acid anhydride.

References Cited UNITED STATES PATENTS 7/1968 Williamson 260-3095 X6/1969 Porret et al 260-309.5

US. Cl. X.R.

117-161 ZB; 260--2 Ep, 78.4 Ep

